Epoxy-Vitrimer Chemistry - ACS Publications - American Chemical

Article pubs.acs.org/Macromolecules

Cross-Linking of Poly(butylene terephthalate) by Reactive Extrusion Using Zn(II) Epoxy-Vitrimer Chemistry Adrien Demongeot,† Ramon Groote,‡ Han Goossens,‡ Theo Hoeks,‡ François Tournilhac,*,† and Ludwik Leibler† †

Matière Molle et Chimie, UMR 7167 CNRS ESPCI Paris, PSL Research University, 10 rue Vauquelin 75005 Paris, France SABIC T&I, Plasticslaan 1, 4612 PX Bergen op Zoom, The Netherlands

‡

S Supporting Information *

ABSTRACT: Poly(butylene terephthalate) (PBT) vitrimers were prepared by reactive extrusion from industrial PBT thermoplastics using Zn(II)-catalyzed addition and transesterification chemistry. PBT thermoplastics are characterized by a high degree of crystallinity, high melting temperature, and high crystallization rate, but right above their melting temperature their mechanical resistance disappears and they show a tendency to drip. We compared −OH and −COOH end-group additions on epoxies in the presence of two different catalysts: 2-methylimidazole (2-MI) and zinc acetylacetonate (Zn(acac)2). With 2-MI, chain extension reactions were efficiently catalyzed in a few minutes at 270 °C, but no gelation was observed. With Zn(acac)2, −COOH addition and transesterification led to efficient cross-linking within a few minutes at 270 °C. Such cross-linked material combines the crystalline properties of PBT and dimensional stability above the melting temperature. PBT materials cross-linked through epoxy-vitrimer chemistry are not soluble. However, compared with radiation cross-linked PBT, vitrimer PBT is processable and can be reshaped and recycled.

■

INTRODUCTION

Vitrimers, the third category of polymer materials, are networks made of chemically cross-linked polymers in which thermally stimulated exchange reactions permit network topology rearrangements while keeping constant the number of bonds and cross-links. In contrast to the two other categories of polymers, i.e., thermoplastics and thermosets, vitrimers combine insolubility and ability to flow when heated. The viscosity of vitrimers is controlled by the rate of the exchange reactions. The first vitrimers1 were based on epoxy−acid and epoxy−anhydride chemistry and Zn(II)-catalyzed transesterification exchanges. Subsequently, a number of monomers and exchange reactions have been used to synthesize vitrimers.2−13 The objective of this study is to show how the original Zn(II)−epoxy chemistry can be applied to synthesize semicrystalline polyester vitrimers from commercial thermoplastic grades by a cross-linking method that can be used on an industrial scale. Our efforts focused on poly(butylene terephthalate) (PBT). The strategy is presented in Figure 1. The formation of a chemically cross-linked polymer network is usually carried out either by reacting monomers with an average functionality greater than two or by cross-linking a preexisting thermoplastic polymer. In both cases, the process passes through a critical stage, the gelation point at which an infinite network is formed. Beyond the gelation threshold the system becomes an insoluble solid with a definite shape. During the synthesis of a vitrimer, a permanent covalent network is also © XXXX American Chemical Society

Figure 1. Flowchart of the chemical concept toward production of cross-linked PBT vitrimers with the help of epoxy vitrimer chemistry.

formed; however, the network can change its topology thanks to exchange reactions. Here, we use transesterification reactions to build the network. At the same time transesterification Received: June 3, 2017 Revised: July 24, 2017

A

DOI: 10.1021/acs.macromol.7b01141 Macromolecules XXXX, XXX, XXX−XXX

Article

Macromolecules

Reactive Mixing. Modified PBT samples were prepared by reactive mixing. Typically, 10 g of well-dried PBT pellets was introduced via a hopper together with the diepoxide (DGEBA, 0−0.4 g), the esterification catalyst (2-MI, 0−5 mg), or trans-esterification catalyst (Zn(acac)2, 0−36 mg), and an antioxidant (Irganox 1010, 10 mg) into a DSM Xplore 15 cm3 twin-screw mini-compounder under a nitrogen flux. The rotor speed and the temperature were set respectively at 60 rpm and 270 °C. The mixing time was typically fixed at 10 min. The axial force exercised on the barrel of the compounder, which can be used to follow qualitatively the change of viscosity, was recorded as a function of the residence time. In some experiments, aliquots of the reactive mixture were taken out from the compounder to perform ex-situ end-group analysis by FTIR spectroscopy. At high loading (3.6 wt %) of diepoxide, part of the reactive mixture was purged out from the compounder after 5 min mixing to keep the axial force under the 8000 N limitation of the equipment. FTIR Spectroscopy. End-group analyses were carried out using the spectroscopic method developed by Ward and Kosky.31−33 Films were prepared by compression molding at 240 °C followed by rapid cooling in iced water, resulting in samples with a thickness between 100 and 300 μm. The films were dried for 16 h at 90 °C before measurements. Samples were investigated by FTIR spectroscopy in transmission in the 4000−400 cm−1 spectral range. First, the zero hydroxyl and carboxyl absorption levels were determined by using a deuterium exchanged sample (obtained by immersion in D2O at 90 °C for 24 h and dried 16 h at 90 °C). Then, the spectra of the PBT materials were analyzed relative to the background level after normalization to take into account the actual thickness of each sample. The absorbance values corresponding to hydroxyl and carboxyl chain end-groups were measured at 3550 and 3270 cm−1, respectively (see Supporting Information, Figure S1). Absolute calibration was done by recording the spectrum of the starting materials for which the end-group concentrations were known. The reactive mixtures used for the model reactions were obtained by dissolving the reagents 4-heptylbenzoic acid, bisphenol A bis(2,3dihydroxypropyl ether), bisphenol A diglycidyl ether, zinc(II) acetylacetonate, and 2-methylimidazole in acetone. Stoichiometric ratios of 1:1 acyl−epoxy, 1:1 primary hydroxyl−epoxy, and 0.05:1 catalyst−epoxy were used. The FTIR spectra were recorded at 4 cm−1 spectral resolution by using a Bruker TENSOR 37 spectrometer equipped with a DTGS detector and fitted with a Specac Golden Gate ATR heating cell. Samples were deposited on the ATR diamond heated at 200 °C, resulting in a quick evaporation of acetone. The disappearance of the 910 cm−1 absorption peak (υCOC epoxy) was monitored at a rate of one spectrum per minute (average of 32 scans) to determine the epoxy conversion (see Figure S2). In order to measure the initial height of the absorption peak and its evolution at short times (99%).23 The radiation-induced cross-linking process is irreversible. It needs to be performed on the parts in their final shape using electron or γ radiation facilities. In this paper, we describe a cross-linking method based on reactive mixing and extrusion.24−30 Usually, in reactive extrusion, precautions are taken to avoid gelation during the process. Indeed gelation can block the extruder. Here, thanks to the exchangeable nature of bonds the composition can be adjusted to ensure the processability during a reactive mixing stage. When necessary, cross-linking can be completed after reactive mixing in a curing step.

■

EXPERIMENTAL SECTION

Materials. Two different PBT materials, specifically synthesized for this study, were obtained from SABIC. One referred to as “high PBT” has molar masses of Mn = 47 kg/mol and Mw = 100 kg/mol as well as end-group concentrations of [COOH] = 37 mequiv/kg and [OH] = 23 mequiv/kg. The other, referred to as “low PBT”, has Mn = 23 kg/ mol and Mw = 48 kg/mol as well as [COOH] = 17 mequiv/kg and [OH] = 120 mequiv/kg. Before use, PBT pellets were dried for 16 h at 120 °C under vacuum. Diglycidyl ether of bisphenol A (DGEBA), with an [OH]/epoxy ratio lower than 0.03, and an oligo-bisphenol A-co-epichlorohydrine solid epoxy resin, with an [OH]/epoxy of approximately 1.2, both produced by the Dow Chemical Company were used. 2Methylimidazole (99%), NaCl (99%), ethyl acetate (99.5%), 3chloro-1,2-propanediol (98%), pentaerythritol tetrakis(3,5-ditert-butyl4-hydroxyhydrocinnamate) (Irganox 1010, 98%), and bisphenol A (99%) were purchased from Sigma-Aldrich. Zinc(II) acetylacetonate (Zn(acac)2) (23.5−26.0 wt % Zn) was purchased from Acros Organics. 1,1,2,2-Tetrachloroethane (98%), sodium hydroxide pellets (98%), hydrochloric acid, 36% w/w aqueous solution, and 4heptylbenzoic acid were purchased from Alpha Aesar. These products were used as received. The synthesis of bisphenol A bis(2,3dihydroxypropyl) ether is described in the Supporting Information. B


Article

Macromolecules Table 1. Characteristics of Prepared Blends starting material

catalyst

compd

Mna (kg/mol)

[epoxy]/([OH] + [COOH])

DGEBA quantity (wt %)

type

[catalyst]/([OH] + [COOH])

mixing time (min)

insoluble fraction (%)

1 2a 2d 3a 3d 4a 4b 4c 4d 5 6

47 47 47 47 47 47 47 47 47 47 23

0 1.0 3.4 1.0 3.4 1.0 1.2 1.7 3.4 1.7 1.7

0 1.1 3.6 1.1 3.6 1.1 1.3 1.7 3.6 1.7 4.2

none none none 2-MI 2-MI Zn(acac)2 Zn(acac)2 Zn(acac)2 Zn(acac)2 Zn(acac)2 Zn(acac)2

0 0 0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

10 10 10 10 10 10 10 10 10 2c 2c

0 0 0 0 0 4 38 43 75 0 0

E′b (kPa)

5 equiv/kg and [OH]/[ester] > 2. In our case, however, monitoring of [OH] gives concentrations not exceeding 100 mequiv/g, i.e., an [OH]/[ester] ratio of the order of 0.01. It is therefore unlikely that dehydration could play an important role. Still, for long reaction times when transesterification is not catalyzed, it could eventually contribute to some cross-linking. 3.2. Vitrimer Network Properties. Reactive mixing of diepoxy and PBT polymers yields permanent networks when mixing is performed in the presence of Zn(II) catalyst. The solubility tests indicate that cross-linking degree increases when the diepoxy fraction is increased. For example, when the fraction of DGEBA varies from 1.2 to 3.6 wt %, the insoluble fraction increases from 4 to 75 wt %. The increase of crosslinking density with diepoxy fraction is also confirmed by the DMTA experiments at 1 Hz. Above the melting temperature a plateau modulus is observed for high diepoxy contents, and it varies between 0.15 and 0.8 MPa when the diepoxy fraction varies from 1.7 to 3.6 wt %. It is not necessary to carry out the reactive mixing step to complete reaction. Isothermal curing after a short reactive mixing time at temperatures above the melting temperature can be used to increase the cross-linking degree as demonstrated by rheology and solubility experiments (Figure 3). These experiments combined with kinetic studies (Figure 2) show that the molecular weight of the precursor PBT gives an additional handle to control the cross-linking degree. For the high molecular weight PBT, the number of −OH and −COOH groups is low, and the same molar fraction of epoxy leads to a less cross-linked material. Interestingly, cross-linking does not perturb crystallization. The crystallization is fast, and the degree of crystallinity is basically maintained (Figure 4A). In contrast to PBT cross-linked by irradiation, PBT crosslinked by Zn(II) epoxy-vitrimer chemistry can flow above the melting temperature. As an example, Figure 7 shows the stress relaxation results and the variation of viscosity as a function of temperature for compound 4c. Figure 7B shows an Arrhenius dependence ln(η) ∼ 1/T, as hitherto observed in vitrimers. The value of the activation energy is of about 140 kJ/mol.

In the presence of catalysts, the situation is more complex (Figure 2). During the mixing the axial force increases, indicating the increase of viscoelasticity of the mixture (Figure 2C). When 2-MI is used as a catalyst (Figure 2, open blue triangles), the increase of axial force is moderate. The consumption of −COOH groups and increase of −OH groups show that chain extension through addition reactions (Schemes 2A and 2B) occurs. In principle, branching and cross-linking from lateral hydroxyl groups produced during addition reactions could also occur (Scheme 2C). Solubility tests show that after mixing all samples were soluble (Table 1). We conclude that 2-MI catalyst is very efficient to promote esterification and etherification. However, it is not very efficient to promote transesterification. As a result, it is not efficient to promote formation of a permanent network. In contrast to 2-MI, when Zn(II) catalyst is used, a particularly abrupt increase of the axial force is observed after a few minutes of mixing. The solubility studies demonstrate formation of a permanent network (Table 1). The study of −COOH and −OH variations (Figures 2A and 2B) seem to indicate that Zn(II) promotes chain extension less efficiently than 2-MI. Studies of model molecules confirm this observation. They also indicate that Zn(II) promotes fast transesterification. The increase of axial force, an indication of cross-linking, seems to occur only when a large fraction of the initially present −COOH groups is consumed. Addition reactions lead to formation of both ester bonds and lateral hydroxyl groups. As a result, Zn(II) catalyst is able to induce G


Article

Macromolecules

no evidence of any terminal regime down to an angular frequency of 10−2 s−1. Indeed, for this compound, the relaxation time given by stress relaxation experiments is much larger than 100 s. Figures 8B and 8C illustrate the good dimensional stability of vitrimers in comparison with standard PBT. We show the appearance of compression-molded coin-sized specimens made of these two materials after a residence times of 3 and 30 min, respectively, in an oven at 250 °C in air. After 3 min in the oven, both samples have become transparent, but pristine PBT immediately flows, whereas the shape of the PBT vitrimer part is retained. Under its own weight a coin-sized specimen undergoes a stress of about ρgh ∼ 100 Pa, where ρ is the density of the polymer, g the gravitational acceleration, and h the height of the specimen. With a viscosity of 200 Pa·s the expected strain rate γ̇ = σ/η is of about 0.5 s−1. Thus, without surprise, the coin shape is not recognizable after 3 min. For the vitrimer PBT part, however, the strain rate is approximately γ̇ = 10−6 s−1, and deformation is hardly detectable on this time scale. The fixed shape is also a demonstration that the compression-molded part was thoroughly relaxed. The same two samples after 30 min are shown in Figure 8C. Pristine PBT has dripped outside the framing field, but the vitrimer PBT is still in place. One can see in the picture that after 30 min at 250 °C in some oxidation took place, as shown by the brownish color, but interestingly the shape of the specimen is not much altered. Thus, similarly to radiation cross-linked PBT, PBT cross-linked with the help of epoxy-vitrimer chemistry can handle high temperatures for a relatively long time, whereas the standard PBT flows immediately above the melting temperature.

Figure 7. (A) Plots of stress relaxation experiments on compound 4c. (B) Variation of the viscosity as a function of inverse temperature 1000/T showing Arrhenius dependence.

■

The elastic modulus above Tm, viscosity, and relaxation time can be tuned by the amount of diepoxy. Thus, the relaxation time at 230 °C is 500 s for compound 4c and 1300 s for compound 4d. The long relaxation times above the melting temperature bring good dimensional stability to PBT vitrimers. For the PBT with highest cross-linking, compound 4d, the value of viscosity is about η ∼ 108 Pa·s at 250 °C. This value is huge in comparison with the viscosity of standard PBT, which ranges from 30 to 900 Pa·s at 250 °C.16 The frequency sweep experiments illustrate nicely this difference (Figure 8A). At 250 °C, PBT before modification shows the characteristics of a nonentangled polymer melt. The value of viscosity, inferred from the G″(ω) ∼ ω terminal regime variation, is approximately 200 Pa·s. At the same temperature, the vitrimer PBT (compound 4d) shows elastomeric plateau properties with

CONCLUSION Research and development of vitrimers confronts two challenges. The first challenge concerns the translation of unique combination of vitrimer properties into novel materials and applications. Literature on design of weldable long fiber composites56−58 and nanocomposites,59 photoresponsive carbon-nanotube composites,60,61 UV-curable thiol−ene vitrimers for patterning and nanoimprint lithography,62 moldable and multifunctional liquid-crystalline elastomer actuators,63,64 and shape memory polymer networks65−69 show some interesting directions and potential uses. The second challenge is to develop dynamic covalent chemistries that will allow bringing vitrimer properties to currently produced thermoplastics and

Figure 8. (A) Angular frequency dependence of storage modulus G′ (filled symbol) and loss modulus G″ (open symbols) at 250 °C for PBT (circles), compound 4d (squares). (B) Appearance of PBT and compound 4d disks after 3 min in an oven at 250 °C. (C) Appearance of PBT and compound 4d disks after 30 min in an oven at 250 °C. H


Article

Macromolecules ORCID

thermosets. Developments in the area of fully bio-based vitrimers,2,10,70 amorphous polyesters,4 polyurethanes and polyureas7,12,69,71,72 or polymers with C−C backbones13,73 are promising examples. In this article, we have developed a semicrystalline PBT vitrimer via an industrial process, reactive mixing, starting from standard base materials, i.e., PBT thermoplastic, and an epoxy resin. Epoxy chemistry is particularly convenient as it allows chain extension and branching without release of small molecules. In principle, reacting PBT with multifunctional alcohols could also yield a PBT dynamic network. However, to advance the reaction, small molecules have to be eliminated and a different synthetic route, solid-state polymerization (SSP), is better adapted for this purpose.74 The PBT vitrimers obtained through reactive mixing with diepoxides retain the properties of PBT thermoplastics such as a high degree of crystallinity, while they gain the properties of a cross-linked material such as dimensional stability above melting temperature. Indeed, in contrast to PBT thermoplastics, above melting temperature PBT vitrimers exhibit a rubbery elastic plateau and relax stresses only after a long time. The rubbery plateau and stress relaxation times can be tuned by adjusting the molecular weight of the starting materials and the amount of cross-linker used. The same is true for PBT vitrimers obtained by SSP and both types of materials were found to show an Arrhenius dependence of viscosity with very close Ea values. Interestingly, PBT vitrimers can be obtained within a few minutes by reactive mixing whereas several hours are necessary by SSP. When reactions are completed, both types of materials show a slight yellowish aspect due to the presence of the Zn(II) catalyst. We have shown that alcohol−epoxy and acid−epoxy addition reactions and transesterification reactions, which determine the relative kinetics of chain extension, chain branching, and crosslinking, can be conveniently controlled by the choice of a catalyst, the molecular weight of precursor PBT chains, and the diepoxide content. In terms of industrial processing, such a control provides tools to combine an optimal and versatile manner of extrusion, object molding, and thermal postcuring steps. In particular, it is possible to find conditions that avoid long residence time in the extruder and high viscosity during injection molding. In conclusion, vitrimer epoxy based chemistry yields a versatile method to permanently cross-link semicrystalline PBT thermoplastics without a need to use radiation chemistry facilities. Cross-linked PBT vitrimers can be reshaped and welded. Advantageous properties of PBT vitrimers bode well for their industrial applications for example in electric appliances and electronics for which keeping the integrity of electrical insulation in the case of accidental overheating is essential.

■

François Tournilhac: 0000-0002-6775-1584 Notes

The authors declare no competing financial interest.

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.7b01141. Figures S1−S6, Table S1, and Scheme S1 (PDF)

■

REFERENCES

(1) Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Silica-Like Malleable Materials from Permanent Organic Networks. Science 2011, 334 (6058), 965−968. (2) Lu, Y.-X.; Tournilhac, F.; Leibler, L.; Guan, Z. Making Insoluble Polymer Networks Malleable via Olefin Metathesis. J. Am. Chem. Soc. 2012, 134 (20), 8424−8427. (3) Altuna, F. I.; Pettarin, V.; Williams, R. J. Self-healable polymer networks based on the crosslinking of epoxidised soybean oil by an aqueous citric acid solution. Green Chem. 2013, 15 (12), 3360−3366. (4) Brutman, J. P.; Delgado, P. A.; Hillmyer, M. A. Polylactide Vitrimers. ACS Macro Lett. 2014, 3 (7), 607−610. (5) Imbernon, L.; Oikonomou, E. K.; Norvez, S.; Leibler, L. Chemically crosslinked yet reprocessable epoxidized natural rubber via thermo-activated disulfide rearrangements. Polym. Chem. 2015, 6, 4271−4278. (6) Romano, F.; Sciortino, F. Switching Bonds in a DNA Gel: An AllDNA Vitrimer. Phys. Rev. Lett. 2015, 114, 078104. (7) Denissen, W.; Rivero, G.; Nicolaÿ, R.; Leibler, L.; Winne, J. M.; Du Prez, F. E. Vinylogous Urethane Vitrimers. Adv. Funct. Mater. 2015, 25, 2451−2457. (8) Obadia, M. M.; Mudraboyina, B. P.; Serghei, A.; Montarnal, D.; Drockenmuller, E. Reprocessing and Recycling of Highly CrossLinked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds. J. Am. Chem. Soc. 2015, 137 (18), 6078−6083. (9) Imbernon, L.; Norvez, S.; Leibler, L. Stress Relaxation and SelfAdhesion of Rubbers with Exchangeable Links. Macromolecules 2016, 49, 2172−2178. (10) Imbernon, L.; Norvez, S. From Landfilling to Vitrimer Chemistry in Rubber Life Cycle. Eur. Polym. J. 2016, 82, 347−376. (11) Chen, Q.; Yu, X.; Pei, Z.; Yang, Y.; Wei, Y.; Ji, Y. Multi-stimuli responsive and multi-functional oligoaniline-modified vitrimers. Chem. Sci. 2017, 8, 724−733. (12) Denissen, W.; Droesbeke, M.; Nicolaÿ, R.; Leibler, L.; Winne, J. M.; Du Prez, F. E. Chemical control of the viscoelastic properties of vinylogous urethane vitrimers. Nat. Commun. 2017, 8, 14857−1−7. (13) Röttger, M.; Domenech, T.; van der Weegen, R.; Breuillac, A.; Nicolaÿ, R.; Leibler, L. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis. Science 2017, 356, 62−65. (14) Fakirov, S. Handbook of Thermoplastic Polyesters: Homopolymers, Copolymers, Blends, and Composites; Wiley-VCH Verlag GmbH: Weinheim, 2002. (15) Bernnat, A.; Eibeck, P.; Dirlenbach, J. Polybutylenterephtalat (PBT). Kunststoffe 2013, 10, 106−110. (16) Gallucci, R. R.; Patel, B. R. In Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters; Scheirs, J., Long, T. E., Eds.; John Wiley & Sons: Chichester, 2003; pp 293−322. (17) Antić, V. V.; Pergal, M. V. In Handbook of Engineering and Specialty Thermoplastics: Polyethers and Polyesters; Thomas, S., Visakh, P. M., Eds.; John Wiley & Sons: Hoboken, NJ, 2011; Vol. 3, pp 127− 180. (18) Miller, S. Macrocyclic polymers from cyclic oligomers of poly(butylene terephthalate). Ph.D. Dissertation, University of Massachusetts, Amherst, 1998; p 139. (19) Wypych, G. Handbook of Polymers; ChemTec Publishing: Oxford, 2012. (20) Cleland, M. R.; Parks, L. A.; Cheng, S. Applications for radiation processing of materials. Nucl. Instrum. Methods Phys. Res., Sect. B 2003, 208, 66−73. (21) Rouif, S. Radiation cross-linked polymers: Recent developments and new applications. Nucl. Instrum. Methods Phys. Res., Sect. B 2005, 236 (1), 68−72.

AUTHOR INFORMATION

Corresponding Author

*E-mail [email protected] (F.T.). I


Article

Macromolecules

(43) Bikiaris, D. N.; Karayannidis, G. P. Chain extension of polyesters PET and PBT with two new diimidodiepoxides. II. J. Polym. Sci., Part A: Polym. Chem. 1996, 34 (7), 1337−1342. (44) Xie, F.; Zhou, C.; Yu, W.; Wu, D. Study on the reaction kinetics between PBT and epoxy by a novel rheological method. Eur. Polym. J. 2005, 41 (9), 2171−2175. (45) Japon, S.; Boogh, L.; Leterrier, Y.; Månson, J.-A. Reactive processing of poly(ethylene terephthalate) modified with multifunctional epoxy-based additives. Polymer 2000, 41 (15), 5809−5818. (46) Testud, B.; Pintori, D.; Grau, E.; Taton, D.; Cramail, H. Hyperbranched polyesters by polycondensation of fatty acid-based ABn-type monomers. Green Chem. 2017, 19, 259−269. (47) Pire, M.; Lorthioir, C.; Oikonomou, E. K.; Norvez, S.; Iliopoulos, I.; Le Rossignol, B.; Leibler, L. Imidazole-accelerated crosslinking of epoxidized natural rubber by dicarboxylic acids: a mechanistic investigation using NMR spectroscopy. Polym. Chem. 2012, 3 (4), 946−953. (48) Pire, M.; Norvez, S.; Iliopoulos, I.; Le Rossignol, B.; Leibler, L. Imidazole-promoted acceleration of crosslinking in epoxidized natural rubber/dicarboxylic acid blends. Polymer 2011, 52 (23), 5243−5249. (49) Sordo, F.; Mougnier, S.-J.; Loureiro, N.; Tournilhac, F.; Michaud, V. Design of Self-Healing Supramolecular Rubbers with a Tunable Number of Chemical Cross-Links. Macromolecules 2015, 48 (13), 4394−4402. (50) Blank, W. J.; He, Z. A.; Picci, M. Catalysis of the epoxy-carboxyl reaction. J. Coat. Technol. 2002, 74 (926), 33−41. (51) Merfeld, G.; Molaison, C.; Koeniger, R.; Acar, A. E.; Mordhorst, S.; Suriano, J.; Irwin, P.; Warner, R. S.; Gray, K.; Smith, M.; et al. Acid/ epoxy reaction catalyst screening for low temperature (120°C) powder coatings. Prog. Org. Coat. 2005, 52 (2), 98−109. (52) Capelot, M.; Unterlass, M. M.; Tournilhac, F.; Leibler, L. Catalytic Control of the Vitrimer Glass Transition. ACS Macro Lett. 2012, 1 (7), 789−792. (53) Capelot, M.; Montarnal, D.; Tournilhac, F.; Leibler, L. MetalCatalyzed Transesterification for Healing and Assembling of Thermosets. J. Am. Chem. Soc. 2012, 134 (18), 7664−7667. (54) Demongeot, A.; Mougnier, S.-J.; Okada, S.; Soulié-Ziakovic, C.; Tournilhac, F. Coordination and Catalysis of Zn2+ in Epoxy-Based Vitrimers. Polym. Chem. 2016, 7, 4486−4493. (55) Capelot, M. Chimie de Polycondensation, Polymères Supramoléculaires et Vitrimères. Ph.D. Dissertation, University Pierre and Marie Curie, Paris, 2013; p 91. (56) Chabert, E.; Vial, J.; Cauchois, J.-P.; Mihaluta, M.; Tournilhac, F. Multiple Welding of Long Fiber Epoxy Vitrimer Composites. Soft Matter 2016, 12, 4838−4845. (57) Ruiz de Luzuriaga, A.; Martin, R.; Markaide, N.; Rekondo, A.; Cabañ ero, G.; Rodríguez, J.; Odriozola, I. Epoxy resin with exchangeable disulfide crosslinks to obtain reprocessable, repairable and recyclable fiber-reinforced thermoset composites. Mater. Horiz. 2016, 3 (3), 241−247. (58) Taynton, P.; Ni, H.; Zhu, C.; Yu, K.; Loob, S.; Jin, Y.; Qi, H. J.; Zhang, W. Repairable Woven Carbon Fiber Composites with Full Recyclability Enabled by Malleable Polyimine Networks. Adv. Mater. 2016, 28, 2904−2909. (59) Legrand, A.; Soulié-Ziakovic, C. Silica−Epoxy Vitrimer Nanocomposites. Macromolecules 2016, 49 (16), 5893−5902. (60) Yang, Y.; Pei, Z.; Zhang, X.; Tao, L.; Wei, Y.; Ji, Y. Carbon nanotube−vitrimer composite for facile and efficient photo-welding of epoxy. Chem. Sci. 2014, 5 (9), 3486−3492. (61) Yang, Y.; Pei, Z.; Li, P.; Wei, Y.; Ji, Y. Making and Remaking Dynamic 3D Structures by Shining Light on Flat Liquid Crystalline Vitrimer Films without a Mold. J. Am. Chem. Soc. 2016, 138, 2118− 2121. (62) Lyon, G. B.; Cox, L. M.; Goodrich, J. T.; Baranek, A. D.; Ding, Y.; Bowman, C. N. Remoldable Thiol−Ene Vitrimers for Photopatterning and Nanoimprint Lithography. Macromolecules 2016, 49, 8905−8913.

(22) Mizera, A.; Manas, M.; Manas, D.; Holik, Z.; Stanek, M.; Navrátil, J.; Bednarik, M. Tensile Behaviour of Modified PBT by Radiation Cross-Linking. Adv. Mater. Res. 2014, 1025-1026, 256−260. (23) Hooshangi, Z.; Feghhi, S. A. H.; Sheikh, N. The effect of electron-beam irradiation and halogen-free flame retardants on properties of poly butylene terephthalate. Radiat. Phys. Chem. 2015, 108, 54−59. (24) Koning, C.; Van Duin, M.; Pagnoulle, C.; Jerome, R. Strategies for Compatibilization of Polymer Blends. Prog. Polym. Sci. 1998, 23 (4), 707−757. (25) Orr, C. A.; Cernohous, J. J.; Guegan, P.; Hirao, A.; Jeon, H. K.; Macosko, C. W. Homogeneous reactive coupling of terminally functional polymers. Polymer 2001, 42 (19), 8171. (26) Pernot, H.; Baumert, M.; Court, F.; Leibler, L. Design and properties of co-continuous nanostructured polymers by reactive blending. Nat. Mater. 2002, 1 (1), 54−58. (27) Jeon, H. K.; Macosko, C. W.; Moon, B.; Hoye, T. R.; Yin, Z. Coupling Reactions of End- vs Mid-Functional Polymers. Macromolecules 2004, 37 (7), 2563−2571. (28) Ruzette, A.-V.; Leibler, L. Block copolymers in tomorrow’s plastics. Nat. Mater. 2005, 4 (1), 19−31. (29) Freluche, M.; Iliopoulos, I.; Flat, J.-J.; Ruzette, A.-V.; Leibler, L. Self-organized materials and graft copolymers of polymethylmethacrylate and polyamide-6 obtained by reactive blending. Polymer 2005, 46 (17), 6554−6562. (30) Corte, L.; Rebizant, V.; Hochstetter, G.; Tournilhac, F.; Leibler, L. Toughening with Little Stiffness Loss: Polyamide Filled with ABC Triblock Copolymers. Macromolecules 2006, 39 (26), 9365−9374. (31) Ward, I. M. The measurement of hydroxyl and carboxyl end groups in polyethylene terephthalate. Trans. Faraday Soc. 1957, 53, 1406−1412. (32) Patterson, D.; Ward, I. M. The assignment of the carboxyl and hydroxyl absorptions in the infra-red spectrum of polyethylene terephthalate. Trans. Faraday Soc. 1957, 53, 291−294. (33) Kosky, P. G.; McDonald, R. S.; Guggenheim, E. A. Determination of end-group concentrations and molecular weight of poly(butylene terephthalate) by solid-state fourier transform infrared spectroscopy. Polym. Eng. Sci. 1985, 25 (7), 389−394. (34) Bikiaris, D. N.; Karayannidis, G. P. E. Effect of carboxylic end groups on thermooxidative stability of PET and PBT. Polym. Degrad. Stab. 1999, 63 (2), 213−218. (35) Lum, R. M. Thermal decomposition of poly(butylene terephthalate). J. Polym. Sci., Polym. Chem. Ed. 1979, 17 (1), 203−213. (36) Passalacqua, V.; Pilati, F.; Zamboni, V.; Fortunato, B.; Manaresi, P. Thermal degradation of poly(butylene terephthalate). Polymer 1976, 17 (12), 1044−1048. (37) Pilati, F.; Manaresi, P.; Fortunato, B.; Munari, A.; Passalacqua, V. Formation of poly(butylene terephthalate): Secondary reactions studied by model molecules. Polymer 1981, 22 (11), 1566−1570. (38) Devroede, J.; Duchateau, R.; Koning, C. E.; Meuldijk, J. The Synthesis of Poly(butylene terephthalate) from Terephthalic Acid, Part I: The Influence of Terephthalic Acid on the Tetrahydrofuran Formation. J. Appl. Polym. Sci. 2009, 114 (4), 2435−2444. (39) Devroede, J.; Duchateau, R.; Koning, C. E. The synthesis of poly(butylene terephthalate) from terephthalic acid, part II: Assessment of the first stage of the polymerization process. J. Appl. Polym. Sci. 2009, 114 (4), 2427−2434. (40) Heise, M. S.; Martin, G. C.; Gotro, J. T. Analysis of gel formation in imidazole-catalyzed epoxies. Polym. Eng. Sci. 1992, 32 (8), 529−534. (41) Heise, M. S.; Martin, G. C. Curing mechanism and thermal properties of epoxy-imidazole systems. Macromolecules 1989, 22 (1), 99−104. (42) Montarnal, D.; Tournilhac, F.; Hidalgo, M.; Leibler, L. EpoxyBased Networks Combining Chemical and Supramolecular HydrogenBonding Crosslinks. J. Polym. Sci., Part A: Polym. Chem. 2010, 48 (5), 1133−1141. J


Article

Macromolecules (63) Pei, Z.; Yang, Y.; Chen, Q.; Terentjev, E. M.; Wei, Y.; Ji, Y. Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds. Nat. Mater. 2013, 13 (1), 36−41. (64) Li, Y.; Rios, O.; Keum, J. K.; Chen, J.; Kessler, M. R. Photoresponsive Liquid Crystalline Epoxy Networks with Shape Memory Behavior and Dynamic Ester Bonds. ACS Appl. Mater. Interfaces 2016, 8, 15750−15757. (65) Pei, Z.; Yang, Y.; Chen, Q.; Wei, Y.; Ji, Y. Regional Shape Control of Strategically Assembled Multishape Memory Vitrimers. Adv. Mater. 2016, 28, 156−160. (66) Zhao, Q.; Zou, W.; Luo, Y.; Xie, T. Shape memory polymer network with thermally distinct elasticity and plasticity. Sci. Adv. 2016, 2 (1), e1501297. (67) Arnebold, A.; Hartwig, A. Fast switchable, epoxy based shapememory polymers with high strength and toughness. Polymer 2016, 83, 40−49. (68) Arnebold, A.; Wellmann, S.; Hartwig, A. Network dynamics in cationically polymerized, crosslinked epoxy resins and its influence on crystallinity and toughness. Polymer 2016, 91, 14−23. (69) Zheng, N.; Fang, Z.; Zou, W.; Zhao, Q.; Xie, T. Thermoset Shape-Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation. Angew. Chem., Int. Ed. 2016, 55, 11421−11425. (70) Altuna, F. I.; Hoppe, C. E.; Williams, R. J. J. Shape memory epoxy vitrimers based on DGEBA crosslinked with dicarboxylic acids and their blends with citric acid. RSC Adv. 2016, 6, 88647−88655. (71) Fortman, D. J.; Brutman, J. P.; Cramer, C. J.; Hillmyer, M. A.; Dichtel, W. R. Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers. J. Am. Chem. Soc. 2015, 137, 14019−14022. (72) Zhang, Y.; Ying, H.; Hart, K. R.; Wu, Y.; Hsu, A. J.; Coppola, A. M.; Kim, T. A.; Yang, K.; Sottos, N. R.; White, S. R.; Cheng, J. Malleable and Recyclable Poly(urea-urethane) Thermosets bearing Hindered Urea Bonds. Adv. Mater. 2016, 28, 7646−7651. (73) Jin, K.; Li, L.; Torkelson, J. M. Recyclable Crosslinked Polymer Networks via One-Step Controlled Radical Polymerization. Adv. Mater. 2016, 28, 6746−6750. (74) Zhou, Y.; Goossens, J. G. P.; Sijbesma, R. P.; Heuts, J. P. A. Poly(butylene terephthalate)/Glycerol-based Vitrimers via Solid-State Polymerization Macromolecules.

K


Epoxy-Vitrimer Chemistry - ACS Publications - American Chemical

Recommend Documents